US6184420B1 - Preparation of unsaturated ketones - Google Patents

Preparation of unsaturated ketones Download PDF

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US6184420B1
US6184420B1 US09/150,925 US15092598A US6184420B1 US 6184420 B1 US6184420 B1 US 6184420B1 US 15092598 A US15092598 A US 15092598A US 6184420 B1 US6184420 B1 US 6184420B1
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formula
stage
catalyst
reaction
ketal
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Joaquim Henrique Teles
Norbert Rieber
Klaus Breuer
Dirk Demuth
Hartmut Hibst
Stefan Kaeshammer
Heinz Etzrodt
Wulf Kaiser
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
    • C07C45/513—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being an etherified hydroxyl group
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

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  • the present invention relates to the preparation of ⁇ , ⁇ -monounsaturated or ⁇ , ⁇ , ⁇ -diunsaturated ketones which are useful fragrances or useful intermediates for the synthesis of natural substances, by the combination of conventional reactions of allyl alcohols or propargyl alcohols with isopropenyl ethers with the formation of ketals of acetone as a byproduct, the isopropenyl ethers being prepared by reacting ketals of acetone with propyne or allene in the gas phase over heterogeneous catalysts and the ketal of acetone, obtained as byproduct, being fed into the stated preparation of the isopropenyl ether.
  • one mole of the corresponding ketal is formed as a byproduct from 2 moles of enol ether used, for example acetone dimethyl ketal from isopropenyl methyl ether used, in accordance with the following equations:
  • R 1 to R 5 are each hydrogen or alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl or aralkyl radicals which are unsubstituted or substituted by oxygen-containing groups, it also being possible for R 1 and R 2 , together with the carbon atom to which they are bonded, to form a 5- or 6-membered ring, and R 6 is alkyl of 1 to 4 carbon atoms.
  • the ketal IV obtained as a byproduct must be converted back into the enol ether III for economic reasons. It is known that this can be done by converting the ketals, either in the liquid phase with acidic catalysts (according to EP 703 211) or in the gas phase over heterogeneous catalysts (according to DE 19 544 450) with elimination of alcohol, into the corresponding enol ethers according to the following equation:
  • R is hydrogen or alkyl and R 6 has the abovementioned meaning.
  • the reaction in the liquid phase according to EP 703 211 requires the use of a dissolved foreign substance, ie. an organic acid, the removal of which from the reaction mixture requires an additional separation step.
  • a dissolved foreign substance ie. an organic acid
  • the process according to DE 19544450 has the advantage of the reaction in the gas phase over a heterogeneous catalyst that requires fairly high temperatures.
  • R 1 , R 2 , R 3 , R 4 and R 5 are each hydrogen or alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl or aralkyl radicals which are substituted or unsubstituted by oxygen-containing groups, it also being possible for R 1 and R 2 together to form a 5- or 6-membered ring, which comprises the combination of the following reactions:
  • R 6 is alkyl having 1 to 4 carbon atoms, with formation of a ketal of the formula IV
  • R 6 has the abovementioned meaning, as a byproduct
  • stage (a) The reaction of stage (a) is described in detail in the technical literature and is claimed in the present invention not for itself, but in combination with steps (b) and (c):
  • stage (a) The conditions in stage (a) are described in DE 1193490 or U.S. Pat. No. 3,029 287 or the stated publications in Helv. Chim. Acta. In this context, the information in these patent publications and literature publications are hereby expressly incorporated by reference.
  • stage (a) are in general not critical for carrying out the novel combination process and can of course also be varied, for example by the choice of the catalyst and, if required, of the starting materials.
  • Preferred starting materials of the formula IIa are in particular tertiary allyl alcohols, R 1 preferably being a saturated or unsaturated, branched or straight-chain alkyl radical which is unsubstituted or substituted by oxygen-containing groups, e.g. methoxy or ethoxy groups, an aryl radical or an alkylaryl radical of up to 20 carbon atoms and R 2 is preferably C 1 -C 4 -alkyl, in particular methyl, it also being possible for R 1 and R 2 together to be tetramethylene or pentamethylene which is unsubstituted or substituted by one or more lower alkyl groups, and R 3 , R 4 and R 5 are each hydrogen.
  • R 1 and R 2 together to be tetramethylene or pentamethylene which is unsubstituted or substituted by one or more lower alkyl groups, and R 3 , R 4 and R 5 are each hydrogen.
  • Preferred propargyl alcohols are tertiary propargyl alcohols of the formula IIb where R 1 is a saturated or unsaturated, branched or straight-chain alkyl radical which is unsubstituted or substituted by oxygen-containing groups, or an aryl radical or an alkylaryl radical, each of up to 20 carbon atoms, and R 2 is C 1 -C 4 -alkyl, in particular methyl, it also being possible for R 1 and R 2 together to be tetramethylene or pentamethylene which is unsubstituted or substituted by one or more lower alkyl groups, and R 4 is hydrogen.
  • a particularly suitable isopropenyl ether of the formula III is isopropenyl methyl ether.
  • reaction may be regarded formally as if one mole of an alcohol R 6 OH is transferred from the dialkoxy compound of the formula IV to the acetylene or allene with formation of the enol ether of the formula III.
  • Suitable ketals are the dimethyl, diethyl, di-n-propyl, di-n-butyl and diisobutyl ketals of acetone. 2,2-Dimethoxypropane (acetone dimethyl ketal) is particularly preferred as a starting material.
  • ketals and their preparation from acetone are disclosed in the technical literature. They are obtained, for example, by reacting acetone with the corresponding alcohols or preferably by an addition reaction of alcohols with alkynes or allene, mixtures of enol ethers and the corresponding ketals being obtained, enol ethers being used immediately after the separation of said mixtures and it being possible to feed the ketals to stage (b).
  • Equation 3 (for the reaction of the allyl alcohols as in the Example)
  • mixtures thereof may also be used, especially mixtures as can be isolated, for example, from a C 3 stream of a steamcracker.
  • the reaction of the ketals or acetals with the acetylenes or allenes is carried out in the presence of the heterogeneous catalyst containing zinc or cadmium and silicon and oxygen in the gas phase, either over a fixed bed or in a fluidized bed at from 50 to 400° C., preferably from 100 to 250° C., particularly preferably from 120 to 200° C., and pressures of from 0.1 to 50, in particular from 0.8 to 20, particularly preferably from 0.9 to 10, bar (all pressures are based on the sum of partial pressures of the starting materials).
  • reaction mixture may be diluted with inert gases, such as nitrogen, argon, low molecular weight alkanes or olefins for operational safety or better heat removal.
  • inert gases such as nitrogen, argon, low molecular weight alkanes or olefins for operational safety or better heat removal.
  • the molar ratio of ketal or acetal to alkyne or allene may be from 0.01 to 100, and is preferably from 0.1 to 2, particularly preferably from 0.7 to 1.3.
  • Suitable catalysts containing zinc or cadmium and silicon and oxygen are cadmium silicates and preferably zinc silicates, for example silicates selected from the group consisting of
  • crystalline zinc silicate having essentially the composition and structure of hemimorphite of the formula Zn 4 Si 2 O 7 (OH) 2 ⁇ H 2 O, where the zinc may be present in up to 25% more or less than the stoichiometric amount, and/or
  • X-ray amorphous zinc silicate or cadmium silicate catalysts are obtained, for example, by loading amorphous silica with a zinc salt or cadmium salt and forming the catalyst by thermal treatment.
  • the SiO 2 carrier is at least predominantly amorphous, has a BET surface area from 10 to 1500 m 2 /g, particularly preferably from 100 to 500 m 2 /g and water absorbtivity of from 0.1 to 2, particularly preferably from 0.7 to 1.3 ml/g and can be used in the form of a powder or in the form of prepared moldings.
  • the carrier can furthermore be calcined prior to impregnation. Preferably, however, the carrier is not calcined.
  • the zinc or cadmium compound used is a compound which is soluble in a suitable solvent.
  • Zinc(II) salts which are soluble in water or aqueous ammonia or alcohols, preferably lower alcohols, and whose decomposition temperature is below 400° C. to 500° C. are preferably used.
  • An ammoniacal zinc(II) acetate solution is particularly preferably used for the impregnation. In some cases, it has proven advantageous to carry out the loading with zinc in a plurality of successive impregnations.
  • the catalyst may be brought into the desired form by shaping (for example mixing, kneading and extrusion or pelleting).
  • pore formers may also be used during the shaping (for example superabsorbers, such as Lutexal® (from BASF Ludwigshafen) or Walocel® (methylcellulose/synthetic resin combination, from Wolff, Walsrode)).
  • superabsorbers such as Lutexal® (from BASF Ludwigshafen) or Walocel® (methylcellulose/synthetic resin combination, from Wolff, Walsrode)
  • the zinc or cadmium load may vary within wide limits. Typical values for an uncalcined precatalyst which was prepared by impregnating an SiO 2 carrier with a zinc salt or cadmium salt are, for example, from 1 to 60, preferably from 7 to 30, particularly preferably from 10 to 25, % by weight (calculated in each case as ZnO or CdO) of Zn or Cd.
  • the precatalyst may furthermore be doped with other elements, preferably alkali metals, alkaline earth metals or transition metals.
  • the catalytically active component may be doped with up to 80, preferably up to 50, in particular up to 20, mol percent of further metals selected from the group (A) consisting of beryllium, magnesium, calcium, strontium, barium, manganese, iron, cobalt, nickel and copper and from the group (B) consisting of titanium, zirconium, hafnium, germanium, tin and lead, some of the elements of group (A) replacing zinc or cadmium and some of the elements from group (B) replacing silicon.
  • group (A) consisting of beryllium, magnesium, calcium, strontium, barium, manganese, iron, cobalt, nickel and copper
  • group (B) consisting of titanium, zirconium, hafnium, germanium, tin and lead, some of the elements of group (A) replacing zinc or cadmium and some of the elements from group (B) replacing silicon.
  • the precatalyst can then be calcined at not more than 600° C., in particular from 80 to 300° C., in air or under an inert gas. Calcination at from 120 to 250° C. in air is particularly preferred.
  • forming is preferably carried out, in which the actual active phase is formed in particular on the surface of the catalyst.
  • This solid-state reaction is promoted by the presence of water, alcohols, preferably lower alcohols, or carboxylic acids, preferably lower carboxylic acids, and is therefore advantageously carried out by heating the precatalyst at from 50 to 400° C. in a water- or alcohol-containing atmosphere.
  • the reaction is preferably carried out at from 100 to 250° C. in a water- or methanol-containing gas mixture.
  • the reaction is particularly preferably carried out at from 120 to 200° C.
  • Formation of the active layer is indicated by the increase in the propyne and allene conversion (after from about 5 to 30 minutes, depending on the temperature), by the increase in the selectivity (after from 10 to 300 minutes, depending on the temperature) and by the decline in the concentration of methyl acetate in the exit gas.
  • a steady state (with high propyne or allene conversions) and a high selectivity is reached after from about 2 to 20 hours, depending on the temperature.
  • Standard methods were used for characterizing the catalyst samples (fresh samples as well as samples removed from the reactor).
  • the measured BET surface area which is typically from 10 to 800 m 2 /g, and the hardness are stated in the respective examples. Catalysts having BET surface areas of from 100 to 400 m 2 /g are preferred.
  • the samples were investigated in detail by means of powder X-ray diffractometry (XRD) and transmission electron microscopy (TEM). Neither of the two structure analysis methods reveals any long-range order in the sense of a crystalline structure; all samples were amorphous.
  • the distribution of the zinc over the carrier was investigated on appropriate sections under the electron microscope and by means of a microprobe.
  • the elemental analysis of a zinc acetate/SiO 2 precatalyst shows that the molar C/Zn ratio is dependent on the calcination temperature.
  • Catalysts dried at room temperature have a C/Zn ratio of 3.5 ⁇ 4.
  • the C/Zn ratio is from 1 to 2.
  • the C/Zn ratio decreases even further, as does the catalytic activity of the catalysts formed therefrom.
  • the C/Zn ratio in the precatalyst is 0.02. Active catalyst cannot be formed from this. Since the decomposition of the zinc acetate on the precatalyst is relatively slow, said precatalyst can be exposed to even higher temperatures for short times without the catalytic activity being completely lost.
  • Hemimorphite is a zinc silicate of the formula Zn 4 Si 2 O 7 (OH) 2 ⁇ H 2 O.
  • heterogeneous catalysts which contain, as active component, at least predominantly zinc silicate having the structure of hemimorphite of the formula Zn 4 Si 2 O 7 (OH) 2 ⁇ 2y O y ⁇ x H 2 O, where x and y are from 0 to 1, are suitable for the novel reaction.
  • pure sauconite having the composition Zn 3 Si 4 O 10 (OH) 2 ⁇ n H 2 O forms at a final pH of 5-6.
  • Pure willemite ( ⁇ -Zn 2 SiO 4 ) is obtained at a pH of 6.5-8.5.
  • pure hemimorphite (Zn 4 Si 2 O 7 (OH) 2 ⁇ H 2 O) crystallizes out only in a weakly alkaline medium at pH greater than 10.
  • H. Nagata M. Matsunage and K. Hosokawa (Zairyo-to-Kankyo 42 (1993), 225-233) prepared hemimorphite by reacting aqueous zinc sulfate solution with sodium hydroxide solution and aqueous sodium silicate solution at a pH of 13, isolating the precipitate obtained and washing it thoroughly and ageing it at 85° C. for at least 24 hours.
  • hemimorphite can be prepared from an acid-treated clay mineral and zinc oxide or zinc hydroxide under hydrothermal conditions (170° C., 5 h).
  • the acid pretreatment of the clay is very expensive and this process is therefore disadvantageous.
  • hemimorphite can also be obtained by a hydrothermal reaction of mixtures of ZnO and SiO 2 at 175-200° C. (composition: 3 ZnO+2 SiO 2 ).
  • the product obtained contains predominantly hemimorphite but is contaminated with sauconite (Zn 3 Si 4 O 10 O(OH) 2 ⁇ 4 H 2 O).
  • a preferred novel preparation method is one in which an alkali metal or alkaline earth metal silicate, preferably sodium silicate, is reacted with a zinc salt, in particular zinc nitrate, and a base, such as an alkali metal or alkaline earth metal hydroxide, in particular sodium hydroxide, in aqueous solution at pH of from 4 to 9.5, preferably from 5.5 to 8, in particular at neutral pH, for example, at pH 6-7.5, at from 50 to 100° C., in particular from 70 to 100° C., in the case of atmospheric pressure and at from 100 to 250° C., preferably from 100 to 200° C., in the case of hydrothermal conditions.
  • a base such as an alkali metal or alkaline earth metal hydroxide, in particular sodium hydroxide
  • Pure hemimorphite having a Zn/Si ratio of 2 can be synthesized by this preparation method.
  • hemimorphite preparation having a zinc content up to 25% less than or greater than the stoichiometric amount, corresponding to a Zn : Si atomic ratio of from 1.6 to 2.5, are also obtainable.
  • Hemimorphites which contain 0-20% excess of zinc are preferred as catalysts. Hemimorphites which contain 0-10% excess of zinc are particularly preferred.
  • the hemimorphite products are obtained in the synthesis as white crystalline precipitate in the form of an aqueous suspension and must be separated from the aqueous solution by suitable measures, for example filtration or centrifuging. In the case of filtration, the filter cake obtained is then washed sodium- and nitrate-free and then dried. Drying can be carried out at up to 600° C., preferably from 90 to 250° C.
  • Thermogravimetric investigations have shown that the crystallized hemimorphite of the composition Zn 4 Si 2 O 7 (OH) 2 H 2 O loses increasing proportions of its water of crystallization at from about 100 to 200° C.
  • the OH ⁇ ions present in the hemimorphite are additionally converted into O 2 -ions and eliminated H 2 O (2 OH ⁇ ⁇ H 2 O+O 2 ⁇ ), likewise with retention of the hemimorphite structure, resulting in hemimorphite preparations of the composition Zn 4 Si 2 O 7 (OH) 2 ⁇ 2y O y , where y is from 0 to 1 and increases with increasing temperature.
  • Hemimorphite preparations obtained after drying up to 600° C., preferably from 90 to 450° C., and having the composition Zn 4 Si 2 O 7 (OH) 2 ⁇ 2y O y ⁇ x H 2 O, where x and y are from 0 to 1, are then usually processed by the conventional shaping methods, for example pelleting or extrusion, or are converted into coated catalysts on steatite beads to give catalytic moldings. The details are described in the examples.
  • Standard methods are used for characterizing the catalyst samples (fresh samples as well as samples removed from the reactor).
  • the measured BET surface area is as a rule from 3 to 400 m 2 /g. Catalysts with BET surface areas of from 20 to 300 m 2 /g are preferably used.
  • the samples obtained by the novel preparation process are investigated in detail by means of powder X-ray diffractometry (XRD) and transmission electron microscopy (TEM).
  • XRD powder X-ray diffractometry
  • TEM transmission electron microscopy
  • an aqueous suspension of an alkali metal or alkaline earth metal silicate is reacted with an aqueous solution of a zinc salt
  • the residence time is maintained such that crystallization of the zinc silicate does not yet occur to any considerable extent.
  • the essentially X-ray amorphous zinc silicate thus obtainable contains Zn 2+ ⁇ , Si 4+ and O 2 ⁇ ions; in addition, the compound may contain OH ions and water of hydration.
  • the Zn/Si ratio is from 0.3 to 5, preferably from 1 to 2.7, particularly preferably from 2 to 2.3, very particularly preferably 2.
  • the X-ray amorphous zinc silicate thus has the Zn/Si ratio of crystalline hemimorphite (Zn 4 Si 2 O 7 (OH) 2 ⁇ H 2 O).
  • the precipitated amorphous zinc silicate catalyst to be used according to the invention can also be doped with up to 80, preferably up to 50, in particular up to 20, mol percent of further metals selected from the group (A) consisting of beryllium, magnesium, calcium, strontium, barium, manganese, iron, cobalt, nickel, copper, cadmium and mercury and from the group (B), consisting of titanium, zirconium, hafnium, germanium, tin and lead, the elements of group (A) replacing some of the zinc and the elements of group (B) replacing some of the silicon in the hemimorphite structure.
  • group (A) consisting of beryllium, magnesium, calcium, strontium, barium, manganese, iron, cobalt, nickel, copper, cadmium and mercury
  • group (B) consisting of titanium, zirconium, hafnium, germanium, tin and lead, the elements of group (A) replacing some of the zinc and the elements of group (B) replacing
  • the X-ray amorphous zinc silicate is obtained as a powder in the preparation.
  • This powder can be used as such for the catalytic reaction (for example in a fluidized-bed reactor) or after molding (for example extrusion, pelleting, etc., possibly also with the addition of assistants in a form suitable for a fixed-bed reactor.
  • the catalyst Before use, the catalyst can be calcined at from 80 to 750° C., preferably from 120 to 500° C., particularly preferably from 200 to 400° C. in the air.
  • pore formers may also be added during the shaping, for example during the pelleting or extrusion (for example superabsorbers such as Lutexal P® (from BASF AG) or Walocel® (methylcellulose/synthetic resin combination, from Wolff, Walsrode AG)).
  • stages (a) to (c) can be carried out batchwise or, preferably, continuously.
  • the ketal of the formula IV obtained as a byproduct in stage (a) is collected in a storage container and converted into the enol ether of the formula III, temporarily, and, if required, spatially separately from the process of stage (a).
  • the preparation of the enol ether and the recycling of the ketal to the enol ether preparation stage are spatially integrated in one plant. A very small volume is then required for the buffer container and transport is dispensed with.
  • stage (b) The reaction of stage (b) is carried out as a rule in a tube reactor, the propyne and/or allene (or preferably a mixture composed of 30-43% by volume of propyne, 16-20% by volume of allene, 20-45% by volume of propene, 5-10 by volume of isobutane and 2-6% by volume of propane, obtained by distillation from a side-stream of a steam cracker) were metered in with the ketal under superatmospheric pressure. The starting materials are mixed shortly before the reactor and are let down into the reactor space.
  • the propyne and/or allene or preferably a mixture composed of 30-43% by volume of propyne, 16-20% by volume of allene, 20-45% by volume of propene, 5-10 by volume of isobutane and 2-6% by volume of propane, obtained by distillation from a side-stream of a steam cracker
  • the reaction is carried out as a rule isothermally from 120 to 300° C. and with a feed rate of from 0.5 to 10 mmol/min of propyne and/or allene and from 0.5 to 20 mmol/min of ketal.
  • the reaction pressure is from 0.1 to 50, preferably from 1.1 to 3.5, bar (absolute).
  • stage (b) The enol ether formed in stage (b) is separated from the propene/propane inert gas stream and then purified by distillation. The distilled enol ether is then used in stage (a).
  • the ketal formed as a byproduct in stage (a) is separated from the reacted mixture, if necessary after prior neutralization, by distillation over a column having about 10 theoretical plates at from 100 mbar to 1 bar, preferably from 300 to 800 mbar, and is taken off via the top.
  • the distillate contains excess enol ether III and acetone in addition to the ketal IV.
  • This stream can, in accordance with stage (c), be fed directly into the synthesis of the enol ether or, preferably, be further purified in another column.
  • This column can be operated batchwise or, preferably, continuously.
  • the excess enol ether III is obtained as top product and used directly as a starting material for stage (a).
  • Acetone is removed via a side take-off.
  • the ketal IV is obtained at the bottom and is reacted with propyne/allene to give the enol ether III, in accordance with stage (c).
  • the Zn/SiO 2 supported catalyst was obtained by impregnating X-ray amorphous SiO 2 moldings (beads of diameter 3-6 mm) having a BET surface area of 358 m 2 /g, a water absorbtivity of 0.9 ml/g and a hardness of 43 N/molding with ammoniacal zinc acetate solution.
  • 225 g of SiO 2 carrier Sigel, from Solvay
  • Zn(OAc) 2 ⁇ 2 H 2 O (Merck) dissolved in 220 g of 9% strength NH 4 OH solution at room temperature, and the precatalyst was dried for 16 hours at 120° C.
  • the precatalyst had a BET surface area of 195 m 2 /g and a hardness of 76 N/molding.
  • the acetate/Zn ratio was 0.9 mol/mol.
  • Example 1 Distillation was carried out as in Example 1.147 g of a mixture comprising mainly 2-methoxypropene and 2,2-dimethoxypropane and 213 g of a fraction comprising 1.6% of 3,7,11-trimethyldodec-1-yn-3-ol, 67% of 6,10,14-trimethylpentadeca-4,5-dien-2-one, and 7.3% of 6,10,14-trimethylpentadeca-3,5-dien-2-one were obtained.
  • stage (a) The methoxypropene/2,2-dimethoxypropane/acetone mixture from a plurality of batches was subjected to fractional distillation, the methoxypropene fraction was reused directly for the reaction of stage (a) and the dimethoxypropane fraction was introduced into stage b (see below) as a starting material.
  • a suspension A comprising 1.5 mol of SiO 2 and 0.89 mol of Na was prepared from 4.5 l of demineralized water and 145.1 g of soda water glass powder containing 62.1% by weight of SiO 2 and 19.0% by weight of Na 2 O (from Riedel-de Haen, D-30918 Seelze). Furthermore, 910.7 g of Zn(NO 3 ) 2 ⁇ 6 H 2 O (98% strength) were dissolved in 2.25 l of demineralized water at room temperature, a solution B containing 3 mol of Zn and 6 mol of NO 3 being obtained.
  • an aqueous solution was prepared from 204.4 g of NaOH in 0.225 1 of demineralized water, a solution C having an Na content of 5.11 mol being obtained.
  • the pH of the resulting suspension D was 7.1.
  • the suspension D was heated to 90° C. and stirred at a speed of 200 rpm for 24 hours at this temperature.
  • the suspension was then cooled to room temperature, and a final pH of 7.0 was measured.
  • the white precipitate which crystallized out was filtered off and washed Na-free with demineralized water and the resulting filter cake was dried at 90° C. in a drying oven.
  • the dried white powder was investigated by X-ray diffraction and gave an X-ray powder pattern which corresponded completely to index card 5-0555 of the JCPDS-ICDD index (1995) and thus indicated the preparation of Zn 4 Si 2 O 7 (OH) 2 ⁇ H 2 O.
  • the prepared catalyst had a BET surface area of 26 m 2 /g and a hardness of 6 N/molding.
  • the forerun containing 2,2-diethoxypropane was collected from a plurality of batches and introduced into stage b) as starting material.
  • a suspension A containing 1.0 mol of SiO 2 and 0.59 mol of Na was prepared from 3.0 l of demineralized water and 96.8 g of soda water glass powder containing 62.1% by weight of SiO 2 and 19.0% by weight of Na 2 O (from Riedel-de Haen, D-30918 Seelze), a solution B containing 2.2 mol of Zn and 4.4 mol of NO 3 was prepared from 667.8 g of Zn(NO 3 ) 2 ⁇ 6 H 2 O (98% strength) in 1.5 l of demineralized water at room temperature and an aqueous solution C having an Na content of 3.81 mol was prepared from 152.3 g of NaOH in 0.4 l of demineralized water.
  • the pH of the resulting suspension D was 7.2.
  • the suspension D was heated to 90° C. and stirred at 200 rpm for 24 hours at this temperature. After the suspension had been cooled to room temperature, a final pH of 7.0 was measured.
  • the resulting white precipitate was filtered off and washed Na-free with demineralized water and the filter cake obtained was dried at 90° C. in a drying oven.
  • the dried white powder was investigated by X-ray diffraction and gave an X-ray powder pattern which completely corresponded to index card 5-0555 of the JCPDS-ICDD index (1995) and thus indicated the preparation of Zn 4 Si 2 O 7 (OH) 2 ⁇ H 2 O.
  • the prepared catalyst had a BET surface area of 44 m 2 /g and a hardness of 44 N/molding.
  • the 2,2-dipropoxypropane fraction was fed to stage (b).
  • the dried white powder was investigated by X-ray diffraction and gave an X-ray powder pattern which corresponded to that of FIG. 1 and thus indicated the preparation of predominant amounts of X-ray amorphous zinc silicate in addition to a small amount of crystalline ZnO (index card 5-0664 of the JCPDS-ICDD index (1995)).
  • amorphous zinc silicate prepared as described above and having the composition of hemimorphite were mixed with 20.2 g of zinc stearate and precompacted to give 20 mm pellet, then communicated to chips having a diameter of ⁇ 0.5 mm and then molded to give pellets measuring 4.75 ⁇ 5.2 mm.
  • the catalyst had a BET surface area of 75 m 2 /g and a hardness of 43 N/pellet. A 100 g portion of the catalyst was then calcined at 350° C. for 10 hours in the air.
  • This catalyst had virtually no forming time.
  • the stated conversion and the selectivity were virtually constant from the beginning.
  • the BET surface area was 82 m 2 /g after the calcination and 64 m 2 /g after removal from the reactor.
  • the hardness was 28 N/pellet after calcination and 36 N/pellet after removal from the reactor.
  • hydronerolidol 60 g of an azeotropic mixture of isopropenyl methyl ether and methanol (about 91% of isopropenyl methyl ether) and 248 mg of 75% strength phosphoric acid were combined in a pressure-resistant vessel. After flushing with nitrogen, the reaction mixture was stirred for 8 hours at 150° C. The reacted mixture was neutralized with aluminum triisopropylate and subjected to fractional distillation. 42 g of a mixture comprising 85% of 2,2-dimethoxypropane, 11.3% of acetone, 0.4% of isopropenyl methyl ether and 0.4% of methanol were obtained at atmospheric pressure. At 0.3 mbar, 6,10,14-trimethylpentadeca-5,9-dien-2-one was obtained in a yield of 78%, based on hydronerolidol used.

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002088064A1 (en) * 2001-04-28 2002-11-07 Degussa Ag Process for the preparation of unsaturated ketones
EP1953134A1 (en) * 2007-01-30 2008-08-06 DSM IP Assets B.V. Process for preparing dienones
WO2008092655A1 (en) * 2007-01-30 2008-08-07 Dsm Ip Assets B.V. Process for preparing dienones
WO2012041948A1 (en) * 2010-10-01 2012-04-05 Dsm Ip Assets B.V. Synthesis of peretinoin
CN109534977A (zh) * 2018-12-12 2019-03-29 万华化学集团股份有限公司 一种由炔丙醇合成α,γ-不饱和二烯酮的方法及用于该方法的催化剂
DE112019002562B4 (de) 2019-01-02 2023-03-02 Shandong Nhu Pharmaceutical Co., Ltd. Verfahren zur Herstellung von ungesättigten Ketonen

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004003245A1 (de) * 2004-01-21 2005-08-18 Basf Ag Verfahren zur destillativen Gewinnung von reinen Isopropenylethern
EP2297078B1 (en) * 2008-05-13 2015-08-19 DSM IP Assets B.V. Allyl and propargyl ethers
JP5481712B2 (ja) * 2008-10-21 2014-04-23 ディーエスエム アイピー アセッツ ビー．ブイ． γ、δ−不飽和ケトン類の製造
CN109824478B (zh) * 2019-03-15 2020-12-01 西南化工研究设计院有限公司 一种联产二甲基己炔二醇和双丙酮醇的新工艺

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3029287A (en) 1958-08-01 1962-04-10 Hoffmann La Roche Preparation of unsaturated ketones
GB981702A (en) 1962-07-11 1965-01-27 Hoffmann La Roche The manufacture of ª†,ª€-unsaturated aldehydes and ketones
US3453317A (en) 1962-07-11 1969-07-01 Hoffmann La Roche Unsaturated carbonyl compounds and processes
US3493619A (en) 1968-09-05 1970-02-03 Givaudan Corp Unsaturated carbonyl compounds
EP0165647A2 (en) 1984-06-22 1985-12-27 Mizusawa Industrial Chemicals Ltd. Process for preparation of synthetic crystalline zinc silicate mineral
EP0299286A1 (de) 1987-07-10 1989-01-18 BASF Aktiengesellschaft Verfahren zur Herstellung von Vinylethern
EP0703211A1 (de) 1994-09-23 1996-03-27 Hüls Aktiengesellschaft Verfahren zur Herstellung von ungesättigten Ethern
EP0776879A1 (de) 1995-11-29 1997-06-04 Basf Aktiengesellschaft Verfahren zur Herstellung von Enolethern
DE19649564A1 (de) 1996-11-29 1998-06-04 Basf Ag Verfahren zur Herstellung von gamma,delta-ungesättigter Ketone durch Umsetzung tertiärer Allylalkohole mit Alkenylalkylethern
DE19726667A1 (de) 1997-06-23 1998-12-24 Basf Ag Verfahren zur Herstellung von Enolethern

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD265289A3 (de) * 1984-06-11 1989-03-01 Oleg N Temkin Verfahren zur gewinnung von isopropenylaethern
DD267629A3 (de) * 1985-10-02 1989-05-10 Mo I Tonkoj Khim Technologii Verfahren zur gewinnung von duesopropenylethern

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3029287A (en) 1958-08-01 1962-04-10 Hoffmann La Roche Preparation of unsaturated ketones
GB981702A (en) 1962-07-11 1965-01-27 Hoffmann La Roche The manufacture of ª†,ª€-unsaturated aldehydes and ketones
DE1193490B (de) 1962-07-11 1965-05-26 Hoffmann La Roche Verfahren zur Herstellung von gamma,delta-ungesaettigten Aldehyden oder Ketonen
US3453317A (en) 1962-07-11 1969-07-01 Hoffmann La Roche Unsaturated carbonyl compounds and processes
US3493619A (en) 1968-09-05 1970-02-03 Givaudan Corp Unsaturated carbonyl compounds
EP0165647A2 (en) 1984-06-22 1985-12-27 Mizusawa Industrial Chemicals Ltd. Process for preparation of synthetic crystalline zinc silicate mineral
EP0299286A1 (de) 1987-07-10 1989-01-18 BASF Aktiengesellschaft Verfahren zur Herstellung von Vinylethern
EP0703211A1 (de) 1994-09-23 1996-03-27 Hüls Aktiengesellschaft Verfahren zur Herstellung von ungesättigten Ethern
US5576465A (en) 1994-09-23 1996-11-19 Huels Aktiengesellschaft Process for preparing unsaturated ethers
EP0776879A1 (de) 1995-11-29 1997-06-04 Basf Aktiengesellschaft Verfahren zur Herstellung von Enolethern
DE19544450A1 (de) 1995-11-29 1997-06-05 Basf Ag Verfahren zur Herstellung von Enolethern
US5767325A (en) 1995-11-29 1998-06-16 Basf Aktiengesellschaft Preparation of enol ethers
DE19649564A1 (de) 1996-11-29 1998-06-04 Basf Ag Verfahren zur Herstellung von gamma,delta-ungesättigter Ketone durch Umsetzung tertiärer Allylalkohole mit Alkenylalkylethern
WO1998023570A1 (de) 1996-11-29 1998-06-04 Basf Aktiengesellschaft VERFAHREN ZUR HERSTELLUNG η, δ-UNGESÄTTIGTER KETONE DURCH UMSETZUNG TERTIÄRER ALLYLALKOHOLE MIT ALKENYLALKYLETHERN
DE19726667A1 (de) 1997-06-23 1998-12-24 Basf Ag Verfahren zur Herstellung von Enolethern

Non-Patent Citations (12)

* Cited by examiner, † Cited by third party
Title
A.G. Merkulov et al., "Formation Mechanism of Zinc Silicates", Tr. Soveshch. Eksp. Tekh. Mineral. Petrogr., vol. 8, pp. 332-328, 1971 (with English Abstract).
A.G. Merkulov et al., "Low-Temperature Synthesis of Zinc Silicates", Izv. Sib. Otd. Akad. Nauk SSSR, Ser. Khim. Nauk, vol. 4, pp. 70-74, 1969 (with English Abstract).
Chemical Abstracts, vol. 112, No. 7, Feb. 12, 1990, Abstract No. 54986a, O.N. Temkin et al, "A Catalyst for the Manufacture of Methyl and Ethyl Isopropenhyl Ethers".
Chemical Abstracts, vol. 112, No. 7, Feb. 12, 1990, Abstract No. 54987b, O.N. Temkin et al., "A Catalyst for the Manufacture of Methyl and Ethyl Isopropenyl Ether".
D.M. Roy et al, "Stability of Minerals in the System ZnO-SiO2-H2O1", Econ. Geol., vol. 51, pp. 432-443, 1956.
G. Saucy et al., "Über Die Reaktion Von Tertiären Vinylcarbinolen Mit Isopropenläther Eine Neue Mthode Zur Her Stellung Von gamma, delta-Ungestätigten Ketonen", Helvetica Chimica Acta, vol. 50, pp. 2091-2100, 1967.
G. Saucy et al., "Über Die Reaktion Von Tertiären Vinylcarbinolen Mit Isopropenläther Eine Neue Mthode Zur Her Stellung Von γ, δ-Ungestätigten Ketonen", Helvetica Chimica Acta, vol. 50, pp. 2091-2100, 1967.
G. Saucy et al., "Über Eine Neuartige Synthese Von beta-Ketonallenen Durch Reaktion Von Tertiären Acetylencarbinolen Mit Vinyläthern Eine Ergiebige Methode Zur Darstellung Des Pseudojonons Und Verwandter Verbindungen", Helvetica Chimica Acta, vol. 50, pp. 1158-1167, 1967.
G. Saucy et al., "Über Eine Neuartige Synthese Von β-Ketonallenen Durch Reaktion Von Tertiären Acetylencarbinolen Mit Vinyläthern Eine Ergiebige Methode Zur Darstellung Des Pseudojonons Und Verwandter Verbindungen", Helvetica Chimica Acta, vol. 50, pp. 1158-1167, 1967.
H. Nagata et al., "Analytical Study of the Formation Process of Hemimorphite-Part I-Analysis of the Crystallization Process by the Co-Precipitation Method", Zairyo-to-Kankyo, vol. 42, pp. 225-233, 1993.
P. Taylor et al., "Hydrothermal Synthesis of Zinc Silicates From Borosilicate Glasses and From Mixtures of Zinc Oxide and Silica", Polyhedron, vol. 3, No. 2, pp. 151-155, 1984.
T. Baird et al., "An IR and EM Study of the Reactivity of Some Divalent Metal Hydroxides with Silica Gel", Reactivity of Solids, Proce. Int. Sympos., vol. 8, pp. 337-342, 1977.

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002088064A1 (en) * 2001-04-28 2002-11-07 Degussa Ag Process for the preparation of unsaturated ketones
US6586635B2 (en) 2001-04-28 2003-07-01 Degussa Ag Process for the preparation of unsaturated ketones
EP1953134A1 (en) * 2007-01-30 2008-08-06 DSM IP Assets B.V. Process for preparing dienones
WO2008092655A1 (en) * 2007-01-30 2008-08-07 Dsm Ip Assets B.V. Process for preparing dienones
WO2012041948A1 (en) * 2010-10-01 2012-04-05 Dsm Ip Assets B.V. Synthesis of peretinoin
US8846961B2 (en) 2010-10-01 2014-09-30 Dsm Ip Assets B.V. Synthesis of peretinoin
CN109534977A (zh) * 2018-12-12 2019-03-29 万华化学集团股份有限公司 一种由炔丙醇合成α,γ-不饱和二烯酮的方法及用于该方法的催化剂
CN109534977B (zh) * 2018-12-12 2022-04-22 万华化学集团股份有限公司 一种由炔丙醇合成α，γ-不饱和二烯酮的方法及用于该方法的催化剂
DE112019002562B4 (de) 2019-01-02 2023-03-02 Shandong Nhu Pharmaceutical Co., Ltd. Verfahren zur Herstellung von ungesättigten Ketonen

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